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Names | |||
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Systematic IUPAC name Titanium(IV) hydride | |||
Other names Titanium tetrahydride Titane TiH4 | |||
Identifiers | |||
3D model (JSmol) | |||
ECHA InfoCard | 100.035.414 | ||
EC Number |
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PubChem CID | |||
UN number | 1871 | ||
CompTox Dashboard (EPA) | |||
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Properties | |||
TiH4 | |||
Molar mass | 51.899 g/mol | ||
Appearance | Colourless gas | ||
Reacts | |||
Related compounds | |||
Other anions | Titanium(IV) fluoride Titanium(IV) chloride Titanium(IV) bromide Titanium(IV) iodide | ||
Other cations | Methane Silane Germane Stannane Plumbane | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
Titanium(IV) hydride (systematically named titanium tetrahydride) is an inorganic compound with the empirical chemical formula TiH
4. It has not yet been obtained in bulk, hence its bulk properties remain unknown. However, molecular titanium(IV) hydride has been isolated in solid gas matrices. The molecular form is a colourless gas, and very unstable toward thermal decomposition. As such the compound is not well characterised, although many of its properties have been calculated via computational chemistry.
Titanium(IV) hydride was first produced in 1963 by the photodissociation of mixtures of TiCl4 and H2, followed by immediate mass spectrometry. [1] Rapid analysis was required as titanium(IV) hydride is extremely unstable. Computational analysis of TiH4 has given a theoretical bond dissociation energy (relative to M+4H) of 132 kcal/mole. [2] As the dissociation energy of H2 is 104 kcal/mole the instability of TiH4 can be expected to be thermodynamic; with it dissociating to metallic titanium and hydrogen:
TiH4, along with other unstable molecular titanium hydrides, (TiH, TiH2, TiH3 and polymeric species) has been isolated at low temperature following laser ablation of titanium. [3]
It is suspected that within solid titanium(IV) hydride, the molecules form aggregations (polymers), being connected by covalent bonds. [4] Calculations suggest that TiH4 is prone to dimerisation. [3] This largely attributed to the electron deficiency of the monomer and the small size of the hydride ligands; which allows dimerisation to take place with a very low energy barrier as there is a negligible increase in inter-ligand repulsion.
The dimer is a calculated to be a fluxional molecule rapidly inter-converting between a number of forms, all of which display bridging hydrogens. [4] This is an example of three-center two-electron bonding.
Monomeric titanium(IV) hydride is the simplest transition metal molecule that displays sd3 orbital hybridisation. [5]
A hydrogen bond is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group, and another electronegative atom bearing a lone pair of electrons—the hydrogen bond acceptor (Ac). Such an interacting system is generally denoted Dn–H···Ac, where the solid line denotes a polar covalent bond, and the dotted or dashed line indicates the hydrogen bond. The most frequent donor and acceptor atoms are the second-row elements nitrogen (N), oxygen (O), and fluorine (F).
Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and selenium, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide, cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term "metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. Metal β-diketonates, alkoxides, dialkylamides, and metal phosphine complexes are representative members of this class. The field of organometallic chemistry combines aspects of traditional inorganic and organic chemistry.
A Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, is a catalyst used in the synthesis of polymers of 1-alkenes (alpha-olefins). Two broad classes of Ziegler–Natta catalysts are employed, distinguished by their solubility:
The bond-dissociation energy is one measure of the strength of a chemical bond A−B. It can be defined as the standard enthalpy change when A−B is cleaved by homolysis to give fragments A and B, which are usually radical species. The enthalpy change is temperature-dependent, and the bond-dissociation energy is often defined to be the enthalpy change of the homolysis at 0 K, although the enthalpy change at 298 K is also a frequently encountered parameter.
Borderline hydrides typically refer to hydrides formed of hydrogen and elements of the periodic table in group 11 and group 12 and indium (In) and thallium (Tl). These compounds have properties intermediate between covalent hydrides and saline hydrides. Hydrides are chemical compounds that contain a metal and hydrogen acting as a negative ion.
In organometallic chemistry, agostic interaction refers to the interaction of a coordinatively-unsaturated transition metal with a C−H bond, when the two electrons involved in the C−H bond enter the empty d-orbital of the transition metal, resulting in a three-center two-electron bond. Many catalytic transformations, e.g. oxidative addition and reductive elimination, are proposed to proceed via intermediates featuring agostic interactions. Agostic interactions are observed throughout organometallic chemistry in alkyl, alkylidene, and polyenyl ligands.
A migratory insertion is a type of reaction in organometallic chemistry wherein two ligands on a metal complex combine. It is a subset of reactions that very closely resembles the insertion reactions, and both are differentiated by the mechanism that leads to the resulting stereochemistry of the products. However, often the two are used interchangeably because the mechanism is sometimes unknown. Therefore, migratory insertion reactions or insertion reactions, for short, are defined not by the mechanism but by the overall regiochemistry wherein one chemical entity interposes itself into an existing bond of typically a second chemical entity e.g.:
Transition metal hydrides are chemical compounds containing a transition metal bonded to hydrogen. Most transition metals form hydride complexes and some are significant in various catalytic and synthetic reactions. The term "hydride" is used loosely: some of them are acidic (e.g., H2Fe(CO)4), whereas some others are hydridic, having H−-like character (e.g., ZnH2).
Zinc hydride is an inorganic compound with the chemical formula ZnH2. It is a white, odourless solid which slowly decomposes into its elements at room temperature; despite this it is the most stable of the binary first row transition metal hydrides. A variety of coordination compounds containing Zn–H bonds are used as reducing agents, however ZnH2 itself has no common applications.
Cobalt tetracarbonyl hydride is an organometallic compound with the formula HCo(CO)4. It is a volatile, yellow liquid that forms a colorless vapor and has an intolerable odor. The compound readily decomposes upon melt and in absentia of high CO partial pressures forms Co2(CO)8. Despite operational challenges associated with its handling, the compound has received considerable attention for its ability to function as a catalyst in hydroformylation. In this respect, HCo(CO)4 and related derivatives have received significant academic interest for their ability to mediate a variety of carbonylation (introduction of CO into inorganic compounds) reactions.
Boron monofluoride or fluoroborylene is a chemical compound with formula BF, one atom of boron and one of fluorine. It was discovered as an unstable gas and only in 2009 found to be a stable ligand combining with transition metals, in the same way as carbon monoxide. It is a subhalide, containing fewer than the normal number of fluorine atoms, compared with boron trifluoride. It can also be called a borylene, as it contains boron with two unshared electrons. BF is isoelectronic with carbon monoxide and dinitrogen; each molecule has 14 electrons.
Binary compounds of hydrogen are binary chemical compounds containing just hydrogen and one other chemical element. By convention all binary hydrogen compounds are called hydrides even when the hydrogen atom in it is not an anion. These hydrogen compounds can be grouped into several types.
Cadmium hydride is an inorganic compound with the chemical formula (CdH
2)
n. It is a solid, known only as a thermally unstable, insoluble white powder.
Chromium(II) hydride, systematically named chromium dihydride and poly(dihydridochromium) is pale brown solid inorganic compound with the chemical formula (CrH
2)
n. Although it is thermodynamically unstable toward decomposition at ambient temperatures, it is kinetically metastable.
Iron(I) hydride, systematically named iron hydride and poly(hydridoiron) is a solid inorganic compound with the chemical formula (FeH)
n. It is both thermodynamically and kinetically unstable toward decomposition at ambient temperature, and as such, little is known about its bulk properties.
Iron(II) hydride, systematically named iron dihydride and poly(dihydridoiron) is solid inorganic compound with the chemical formula (FeH
2)
n. ). It is kinetically unstable at ambient temperature, and as such, little is known about its bulk properties. However, it is known as a black, amorphous powder, which was synthesised for the first time in 2014.
A metallocarbohedryne is any one of a family of chemical compounds with the generic molecular formula M
8C
12, where M is a transition metal such as titanium, vanadium, zirconium, niobium, hafnium, molybdenum, chromium, or iron.
Transition metal alkyl complexes are coordination complexes that contain a bond between a transition metal and an alkyl ligand. Such complexes are not only pervasive but are of practical and theoretical interest.
β-carbon elimination is a type of reaction in organometallic chemistry wherein an allyl ligand bonded to a metal center is broken into the corresponding metal-bonded alkyl (aryl) ligand and an alkene. It is a subgroup of elimination reactions. Though less common and less understood than β-hydride elimination, it is an important step involved in some olefin polymerization processes and transition-metal-catalyzed organic reactions.
Metal-ligand cooperativity (MLC) is a mode of reactivity in which a metal and ligand of a complex are both involved in the bond breaking or bond formation of a substrate during the course of a reaction. This ligand is an actor ligand rather than a spectator, and the reaction is generally only deemed to contain MLC if the actor ligand is doing more than leaving to provide an open coordination site. MLC is also referred to as "metal-ligand bifunctional catalysis." Note that MLC is not to be confused with cooperative binding.